Perfluorinated Compounds in Water, Sediment and Soil from Guanting Reservoir, China

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Bull Environ Contam Toxicol (2011) 87:74–79
DOI 10.1007/s00128-011-0307-y
Perfluorinated Compounds in Water, Sediment and Soil
from Guanting Reservoir, China
Tieyu Wang • Chunli Chen • Jonathan E. Naile •
Jong Seong Khim • John P. Giesy • Yonglong Lu
Received: 13 January 2011 / Accepted: 3 May 2011 / Published online: 13 May 2011
Ó Springer Science+Business Media, LLC 2011
Abstract Concentrations of 12 perfluorinated compounds
(PFCs) were measured in 21 representive water, sediment
and soil samples from Guanting Reservoir and vicinity.
Perfluorooctanoic acid (PFOA) was the predominant PFCs
with concentrations of 0.55–2.3 ng/L, \LOQ to 0.68 ng/g
dw and \LOQ to 2.8 ng/g dw in water, sediment and soil,
respectively. Perfluorododecanoic acid (PFDoA) was frequently detected in solid matrices, with concentrations of
\LOQ to 0.18 ng/g dw in sediment and 0.13–0.26 ng/g
dw in soil. PFCs were detected in all environmental
matrices sampled, but concentrations found throughout the
watershed were less than those reported from other
locations.
T. Wang C. Chen Y. Lu (&)
State Key Lab of Urban and Regional Ecology, Research Center
for Eco-Environmental Sciences, Chinese Academy of Sciences,
Beijing 100085, China
e-mail: yllu@rcees.ac.cn
J. E. Naile J. P. Giesy
Toxicology Centre and Department of Veterinary Biomedical
Science, University of Saskatchewan, Saskatoon, SK S7N5B3,
Canada
J. S. Khim
Division of Environmental Science and Ecological Engineering,
Korea University, Seoul 136713, South Korea
J. P. Giesy
Department of Zoology and Center for Integrative Toxicology,
Michigan State University, East Lansing, MI 48824, USA
J. P. Giesy
Zoology Department, College of Science, King Saud University,
P. O. Box 2455, Riyadh 11451, Saudi Arabia
123
Keywords PFOS PFOA Exposure Composition Risk Hazard
Due to their unique amphiphylic properties, perfluorinated
compounds (PFCs) have been used in a variety of applications such as surfactants and surface protectors (Kissa
2001; Giesy and Kannan 2002). Widespread application as
well as environmental persistence and bioaccumulation of
terminal degradation products of PFCs has resulted in
global occurrence in air (Dreyer 2009; Chaemfa et al.
2010); water and sediment (Rayne and Forest 2009); as
well as wildlife (Houde et al. 2006).
Guanting Reservoir (GTR) is Beijing’s second largest
source of water for agricultural and industrial purposes, and
was also used for drinking water until 1997. Since then,
industrial pollution and contamination from farming have
substantially degraded the quality of water in this reservoir.
Contaminations of HCH, DDT, PAHs and metals and
metalloids in water, sediment and soil from this watershed
were reported in previous studies (Wang et al. 2005; Luo
et al. 2007; Jiao et al. 2009). Previous reports have focused
on traditional persistent toxic substances (PTS) with little
information available for emerging PTS such as PFCs.
Concentrations of PFCs in environmental matrices surrounding GTR are scarce. Hence there was a need for a
thorough investigation and assessment of PFCs in water,
sediment and soil around GTR, to determine the critical
contaminants and their sources, so that GTR can be rehabilitated. The objectives of this study were to determine
concentrations and distribution of PFCs in environmental
matrices to identify potential sources, and thus provide
information for future management and remediation efforts
in the GTR.
Bull Environ Contam Toxicol (2011) 87:74–79
Materials and Methods
Each of seven of waters, soils and sediments, totaling 21
samples, were collected from the GTR and surrounding
area during May of 2008 (Fig. 1). One liter of surface
water was collected by dipping a clean, methanol-rinsed
1 L polypropylene (PP) bottle just under the surface of the
water. Residual chlorine in each water sample was reduced
by adding 200 lL of 200 mg/mL of a sodium thiosulfate
solution using a disposable PP syringe. Surface (top
1–10 cm) soil and sediment samples were collected using a
clean methanol rinsed stainless steel trowel. Representative
composites were prepared by mixing five sub-samples from
the area of about 5 m2. Samples were transferred and
stored in clean PP bags. Sample duplicates and field blanks
were collected daily, and were analyzed along with laboratory and procedural blanks. All samples were stored on
ice for transport to the laboratory and frozen at -20°C until
analyses.
Water samples were extracted using Oasis HLB solid
phase extraction cartridges (0.2 g, 6 cm3) (Waters Corp.,
Milford, MA) as previously reported (So et al. 2004).
Cartridges were preconditioned by eluting with 10 mL of
100% methanol followed by 10 mL of nano-pure water at a
rate of 2 drops a second. A 500 mL aliquant of water was
spiked with 500 lL of 5 ng/mL of the internal standard
(PFOS [18O2] and PFOA [1,2,3,413C], [98%, (Wellington
Laboratories, Guelph, ON, Canada) and then loaded onto
the cartridge, at a rate of 1 drop a second. Cartridges were
then washed with 5 mL of 40% methanol in water and
allowed to run dry. Target compounds were eluted with
10 mL of methanol at a rate of 1 drop per second and
collected in a 15 mL PP centrifuge tube. The eluate was
then reduced to 1 mL under a gentle stream of nitrogen
Fig. 1 Sampling locations for soil samples (filled circle), water and
related sediment (filled triangle) around the Guanting Reservoir,
China
75
gas, and filtered using a disposable PP syringe, fitted with
nylon membrane Millex filter unit (pore diameter 0.2 lm,
Whatman, Maidstone, United Kingdom). Soils and sediments were extracted using a method similar to that
described by Higgins et al. (2005). Samples were freezedried, homogenized and passed through a 2.0 mm sieve.
Approximately 1.0 g samples were transferred to a clean
50-mL PP centrifuge tube, and spiked with 500 lL of a
5 ng/mL internal standard, to which 10 mL of a 1% acetic
acid solution was added. Each tube was then vortexed, and
placed in a heated sonication bath for 15 min at 60°C.
After sonication the tubes were centrifuged at 3,000 rpm
for 3 min and the acetic acid solution was decanted into a
new clean 50-mL PP tube. An aliquant of 2.5 mL of a
90:10 (v/v) methanol and 1% acetic acid mixture was then
added to the original vial and the vial was again vortex
mixed and sonicated for 15 min, before being centrifuged
and decanted into the second tube. This process was
repeated once more, and a final 10 mL acetic acid wash
was preformed. All extracts were combined in the second
tube before being passed through the SPE cartridge in a
similar fashion as described above in the water extraction
procedure. Sample extracts were stored and analyzed in PP
auto-sampler vials.
A HP 1200 (Agilent Technologies) high performance
liquid chromatography system (HPLC) was used for separation of all target analytes. The HPLC was fitted with a
Thermo Scientific Betasil C18 (100 9 2.1 mm, 5 lm particle size) analytical column, and a suitable guard column
was used to prevent instrument and elute background
contamination. Ammonium acetate (2 mM) was added as
an ionization aid to methanol which was used as the
mobile phases. Gradient conditions were as follows: Flow
rate of 300 mL/min; 10 lL injection volume; Gradient
began with 60% A (2 mM ammonium acetate) and 40% B
(100% methanol) and was held for 2 min and then ramped
to 20% A at 18 min, held until 20 min, decreased to 0% A
at 21 min, increased to 100% A at 22 min, held until
22.5 min, returned to initial conditions at 23 min, and
finally held constant until 26 min. The temperature of the
column oven was kept constant at 35°C. Mass spectra
were collected using an Applied Biosystems SCIEX 3000
(Foster City, CA) tandem mass spectrometer, fitted with
an electrospray ionization source, operated in negative
ionization mode. Chromatograms were recorded using a
multiple reaction monitoring mode (MRM) with a dwell
time of 40 ms. The following instrument parameters were
used: desolvation temperature (450°C), desolvation (curtain) gas 6.0 arbitrary units (AU); nebulizer gas flow 5
AU; ion spray voltage -3,500 V; and collision gas 12 AU.
The optimal settings for collision energies and declustering potential were determined for each analyte’s
transitions.
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Bull Environ Contam Toxicol (2011) 87:74–79
(2.3 ng/L) and relatively greater concentrations of PFOS
(0.34 ng/L) were observed at G2. This sample was collected from a river in the Beixinpu region, which has
intensive agricultural activities (Orchard and facility agriculture) with significant pesticide applications every year.
Greater concentrations of HCH, DDT and heavy metals
were also observed in soils near this location (Wang et al.
2005; Luo et al. 2007), which suggests local sources of
pollution from agricultural run-off. Location G4, is in a
wetland catchment used to treat industrial and agricultural
runoff from the Yanghe River. The greatest concentration
of PFOS (0.52 ng/L) and greater concentrations of PFOA
(1.8 ng/L) observed at location G4 most likely resulted
from local releases of treated sewage effluents.
Compared to the results of previous studies, concentrations of PFOS and PFOA in water from GTR were slightly
greater than those from the offshore of Japan (0.04–0.07
and 0.14–1.1 ng/L) and oceanic samples including the
Western Pacific Ocean (0.054–0.078 and 0.136–0.142 ng/L),
Central to Eastern Pacific Ocean (0.001–0.02 and
0.015–0.062 ng/L) and North Atlantic Ocean (0.009–0.036
and 0.160–0.338 ng/L) (Yamashita et al. 2005), while
either comparable to or less than those detected in Yichang
(0.29–0.61 and 4.1–4.9 ng/L), Nanjing (0.33–0.38 and
2.1–2.4 ng/L) and Hong Kong (0.09–3.1 and 0.73–5.5 ng/L)
in China (So et al. 2004, 2007) and South Korea coast
(0.04–2.53 and 0.24–11.4 ng/L) (Yamashita et al. 2005). In
the present study, maximum concentrations of PFOS
(0.52 ng/L) and PFOA (2.3 ng/L) were several orders of
magnitude less than those measured in Tokyo Bay, Japan
(0.78–17 and 2.7–63 ng/L) and the Korea coast (4.11–450
and 2.95–68.6 ng/L) (Naile et al. 2010; Sakurai et al.
2010). Although PFOS and PFOA were the predominant
In order to ensure accuracy of sampling, extraction, and
analytical procedures, field blanks were obtained and
analyzed with each set of water samples analyzed. Procedural blanks and recoveries were determined for each set of
extractions. Quantification was performed using the internal standard method based on 18O2-PFOS and 13C4-PFOA
as the surrogate. All field and laboratory blanks were less
than the limit of quantification (LOQ), where the LOQ was
defined as 5 times the background noise. The use of TeflonÒ-coated lab-ware was avoided during all steps of
sample preparation and analysis to minimize contamination
of the samples. HPLC grade methanol and ammonium
acetate were purchased from J.T. Baker (Phillipsburg, NJ,
USA). Analytical grade sodium thiosulfate was purchased
from EMD Chemicals (Gibbstown, NJ, USA). The ions
monitored, method detection limit (MDL), and matrix
spike recoveries for all of the chemicals of interest are
summarized (Table 1).
Results and Discussion
Although 12 PFCs were investigated, only six, PFOS,
PFOA, perfluoroheptanoic acid (PFHpA), perfluorodecanoic acid (PFDA), perfluorododecanoic acid (PFDoA) and
perfluorohexanoic acid (PFHxA) were detected in water
from GTR, PFOS and PFOA were the predominate PFCs in
water (Table 2). Concentrations of PFOS and PFOA ranged from \LOQ to 0.52 ng/L and from \LOQ to 2.3 ng/L,
respectively. The greatest and second greatest concentraP
tions of PFCs (3.1 and 3.0 ng/L) occurred at locations
G2 and G4, with correspondingly greater concentrations of
PFOS and PFOA. The greatest concentration of PFOA
Table 1 Quality assurance of 12 target PFCs including limit of quantification (LOQ), method detection limit (MDL) and matrix spike recovery
(MSR) for water, sediment and soil
Analyte
Acronym
LOQ
MDL
MSR
W (ng/L)
S (ng/g)
W (ng/L)
S (ng/g)
W (%)
S (%)
Perfluorobutanesulfonate
PFBS
0.5
1
1
1
94
32
Perfluorohexanesulfonate
PFHxS
0.1
0.5
0.2
0.5
136
134
Perfluorooctanesulfonate
PFOS
0.1
0.5
0.2
0.5
101
95
Perfluorodecanesulfonate
PFDS
0.1
0.5
0.2
0.5
101
43
Perfluorobutanoic acid
PFBA
1
1
2
1
120
IS
Perfluorohexanoic acid
PFHxA
0.5
0.1
1
0.1
85
79
Perfluoroheptanoic acid
Perfluorooctanoic acid
PFHpA
PFOA
0.5
0.5
0.1
0.5
1
1
0.1
0.5
103
88
123
89
Perfluorononanoic acid
PFNA
1
1
2
1
132
135
Perfluorodecanoic acid
PFDA
0.1
0.1
0.2
0.1
93
106
Perfluoroundecanoic acid
PFUnA
1
0.5
2
0.5
112
53
Perfluorododecanoic acid
PFDoA
1
0.1
2
0.1
77
70
W water; S soil and sediment; IS Insufficient recovery
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Bull Environ Contam Toxicol (2011) 87:74–79
77
Table 2 Concentrations of PFCs in water, sediment and soil samples collected in the Guanting Reservoir area
Sample
PFOS
PFOA
PFHpA
PFNA
PFDA
PFUnA
PFDoA
PFHxS
PFCs
G1
nd
1.1
nd
nd
nd
nd
nd
nd
1.1
G2
0.34
2.3
0.22
nd
nd
nd
0.19
nd
3.1
G3
nd
1.1
nd
nd
nd
nd
nd
nd
1.1
G4
0.52
1.8
0.19
nd
0.23
nd
0.19
nd
3.0
G5
0.14
0.88
nd
nd
nd
nd
0.14
0.19
1.4
G6
nd
0.68
nd
nd
0.18
nd
0.29
nd
1.2
G7
0.15
0.55
nd
nd
nd
nd
nd
nd
0.70
Water (ng/L)
Sediment (ng/g dw)
GS1
nd
0.47
nd
nd
0.21
nd
nd
nd
0.68
GS2
GS3
nd
nd
nd
0.57
nd
nd
nd
nd
nd
0.22
0.18
nd
0.14
0.09
nd
nd
0.32
0.88
GS4
nd
nd
nd
nd
nd
0.12
0.15
nd
0.27
GS5
nd
0.21
nd
nd
nd
nd
0.18
nd
0.39
GS6
nd
0.68
0.35
nd
0.49
nd
0.09
nd
1.6
GS7
nd
nd
nd
nd
0.16
nd
nd
0.53
0.69
GL1
nd
nd
nd
nd
nd
nd
0.19
nd
0.19
GL2
0.86
2.8
1.2
1.4
1.9
0.24
0.13
nd
8.5
GL3
nd
nd
nd
nd
nd
nd
0.13
nd
0.13
GL4
nd
nd
nd
nd
nd
0.10
0.17
nd
0.27
GL5
nd
nd
nd
nd
0.17
0.24
0.26
nd
0.67
GL6
nd
nd
nd
nd
nd
0.32
0.19
nd
0.51
GL7
nd
nd
0.11
nd
nd
0.23
0.13
nd
0.47
Soil (ng/g dw)
nd not detectable, means concentration less than LOQ
PFCs detected in water samples, PFDoA was detected in
approximately 60% of the samples analyzed at concentrations greater than the LOQ, but concentrations of PFDoA
were generally less than those of PFOS and PFOA, with a
threshold of nd 0.29 ng/L. This indicates that in addition to
PFOS and PFOA, PFDoA should be considered in future
monitoring and risk assessments.
Concentrations of PFCs in sediments from GTR were
generally less than the corresponding MDLs (Table 2).
Total concentrations of PFCs ranged from \LOQ to
1.6 ng/g dw. Only PFOA, PFDA, PFUnA, PFDoA and in a
few samples, PFHpA and PFHxS were detected in sediments. PFOA was the dominant PFC observed in sediments
with concentrations ranging from \LOQ to 0.68 ng/g dw.
The greatest concentration of PFOA was observed at
location G6, which is at the mouth of the Yanghe River
where it enters GTR. However, concentrations of PFOA
and PFOS in sediments at locations G2 and G4 were all
less than the LOQ, which suggests that further studies
characterizing transportation and fate between water and
sediment are needed. Compared to the results of previous
studies, concentrations of PFOA in sediments from GTR
were comparable to those from the Huangpu River
(0.20–0.64 ng/g dw) and the Zhujiang River (0.09–
0.29 ng/g dw), China (Bao et al. 2010), and San Francisco
Bay, USA (0.16–0.23 ng/g dw) (Higgins et al. 2005),
whereas they were less than those of the Kyoto River,
Japan (nd 3.9 ng/g dw) (Senthilkumar et al. 2007).
Releases from various PFCs sources not only contaminate surface waters but it also has the ability to contaminate
soils and sediments. PFOS and PFOA have been shown to
absorb onto sediment and sludge (Higgins et al. 2005).
Therefore, soils could be another sink for PFCs. Previous
studies have reported concentrations of PFCs in water,
sediment and biota. However, there are few reports of the
occurrence, distribution, sources and risks of PFCs in soils,
especially in watersheds that are used as a source of
drinking water. Concentrations of PFCs in soils were
generally less than the LOQ, and only one location (G2)
contained detectable PFOS, PFOA, PFHpA, PFNA, PFDA,
PFUnA and PFDoA, with values of 0.86, 2.8, 1.2, 1.4, 1.9,
0.24, 0.13 ng/g dw, respectively. Again, the pervasive
PFCs observed in water and soil at location G2 suggests
possible input either from soil to surface water by runoff or
from surface water to soil by irrigation. PFDoA was
detected in 100% of soils (Table 2), with concentrations
123
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Bull Environ Contam Toxicol (2011) 87:74–79
Recently, Giesy et al. (2010) calculated suggested criteria maximum concentrations (CMC) for sensitive aquatic
species, such as Daphnia magna for PFOS (21 lg/L) and
PFOA (25 mg/L), and criteria continuous concentration
(CCC) for PFOS (5.1 lg/L) and PFOA (2.9 mg/L), as well
as avian wildlife values (AWV) for PFOS (47 ng/L).
Concentrations of PFOA and PFOS in surface water of the
GTR region (all ng/L level) were less than the suggested
allowable concentrations to protect aquatic life. While the
results indicate negligible risk to aquatic wildlife, several
uncertainties on the toxicities of PFCs at less concentration
exist.
Fig. 2 Composition profile of various PFCs in samples from the
Guanting Reservoir (water, sediment and soil from left to right in
each cluster)
ranging from 0.13 to 0.26 ng/g dw. The results are consistent with the fact that PFDoA being found in waters and
sediments, all of which suggest a regional source of
PFDoA. There was no significant difference in trends in
concentrations of PFCs between soils and sediments. In
general, soils and sediments in the GTR contained small
amounts of PFCs. In terms of matrix-dependent accumulation of PFCs, the results of the present study were similar
to those observed previously in South Korea (Naile et al.
2010).
Profiles of relative concentrations of 8 detectable PFCs
are shown (Fig. 2). Samples from the GTR region exhibited completely different profiles among water, sediment
and soils. The ratio of the concentrations of PFOS to PFOA
in water has been applied to identify potential sources of
PFCs. The observation that PFOS/PFOA ratios in water
from GTR were less than 1.0 is consistent with the results
of values observed in South Korea, coastal China, and
Hong Kong (So et al. 2004, 2007). However, the ratios
were different from those reported by Naile et al. (2010)
and Rostkowski et al. (2006), which were typically greater
than 1.0. This indicates local sources of PFOA exist in the
study area. PFOA was the dominant PFC in water, conP
tributing 58%–100% of
PFCs, while the relative contributions of PFOS and other PFCs were less. PFOA was
the predominant PFC in sediments as well, contributed up
P
to 68% of PFCs at location G1. Greater contributions of
PFUnA and PFDoA were observed at locations G2 (54%
and 46%) and G4 (42% and 58%), because neither PFOA
nor PFOS were P
measured at these locations. Relatively
large portions of PFCs were contributed by PFDoA and
PFUnA in soils except for location G2, while concentrations of PFDoA and PFUnA were relatively small compared to other detectable PFCs. This result indicates the
existence of potential sources of PFDoA and PFUnA in the
study area.
123
Acknowledgments This study was supported by the National
Natural Science Foundation of China with Grant No. 41071355,
Environmental Protection Welfare Program under Grant No.
201009032 and the National Basic Research Program of China
(‘‘973’’ Research Program) with Grant No.2007CB407307. Portions
of the research were supported by a Discovery Grant from the
National Science and Engineering Research Council of Canada
(Project No. 326415-07).
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